Process for Removal of Aluminum Oxides from Aqueous Media

ABSTRACT

The present invention relates to the use of lithium salts and/or magnesium salts for the precipitation of aluminum oxides present in aqueous media.

FIELD OF THE INVENTION

The present invention relates to the use of lithium salts and/ormagnesium salts for precipitating aluminum oxides present in aqueousmedia.

BACKGROUND OF THE INVENTION

The process of producing pure alumina from bauxite (the Bayer process)has not significantly changed in the last 100 years. The Bayer processcan be considered in three stages: (1) leaching, (2) precipitation and(3) calcination.

In the leaching stage, aluminum-bearing minerals in bauxite (e.g.,gibbsite, böhmite and diaspore) are selectively leached from insolublecomponents by dissolving them in an aqueous solution of sodiumhydroxide:

(gibbsite): Al(OH)₃+Na⁺+OH⁻→Al(OH)₄ ⁻+Na⁺

(böhmite and diaspore): AlO(OH)+Na⁺+OH⁻+H₂O→Al(OH)₄ ⁻+Na⁺

Before being subjected to the Bayer process, the bauxite ore ispulverized and milled to reduce the particle size, which increases theavailable surface area for contact with the sodium hydroxide. Thecrushed bauxite is then combined with the process liquor and deliveredas a slurry to a heated pressure digester vessel. Conditions within thedigester vessel (e.g., concentration, temperature and pressure) are setaccording to the properties of the bauxite ore. Ores with a highgibbsite content can typically be processed at about 140° C., whileprocessing of ores with a high böhmite content typically requirestemperatures between about 200° C. and about 240° C. The pressure isdefined by the steam pressure during actual process conditions. At 240°C., the pressure is about 35 atmospheres.

After the leaching stage, the insoluble bauxite residue must beseparated from the dissolved alumina-containing liquor by a combinedprocess of precipitation and settling. The liquor is typically purifiedthrough a series of filters before being transferred to theprecipitators.

The alumina in the alumina-containing liquor is precipitated by coolingin the form of aluminum trihydroxide (gibbsite):

Al(OH)₄ ⁻+Na⁺→Al(OH)₃+Na⁺+OH⁻

The gibbsite precipitation step is basically the reverse of the leachingstep, except that the nature of the aqueous media alumina product iscarefully controlled by reaction conditions, including seeding orselective nucleation, precipitation temperature and cooling rate. Duringthe precipitation process sodium hydroxide is regenerated for additionalalumina leaching. The purified crystalline gibbsite, which is alsoreferred to as a hydrate, is then separated from the liquor and calcinedto form alumina for the aluminum smelting process.

2Al(OH)₃→Al₂O₃+H₂O

As the result of Cold War weapons material production, large volumes ofradioactive and chemically hazardous aqueous wastes, which includealuminum oxides, have been generated at the U.S. Department of Energy(DOE) facilities. These wastes are stored in storage tanks at variouslocations, for example the DOE Hanford site in Washington State. Atpresent, the DOE Hanford site stores approximately 53 million gallons ofradioactive aqueous waste in approximately 177 underground tanks. Thiswaste must be processed in the Hanford Waste Tank Treatment andImmobilization Plant (WTP) to immobilize (vitrify) the radioactive wasteconstituents.

One processing problem at the Hanford site relates to the presence ofaluminum oxides (e.g., alumina) in the aqueous waste that forms a sludgethat impairs transfer and processing of the waste. Over 44,00 metrictons of sodium salts are present in the aqueous waste and an additionalestimated 30,000 metric tons of sodium as sodium hydroxide are requiredto leach (i.e., solubilize) insoluble alumina sludge. This additionalamount of sodium salts increases both the glass volume and treatmentschedule at the WTP. Further, soluble alumina can plug WTP processequipment by forming amorphous gels during any of a number of processes(e.g., filtration, ion-exchange, cooling, dilution and/orneutralization) utilized in WTP operations.

The inventors have discovered that the addition of lithium salts and/ormagnesium salts to aqueous media containing aluminum oxides results inthe formation of low solubility lithium-aluminate complexes and/ormagnesium-aluminate complexes that provide a quick and effective way ofseparating soluble alumina from the aqueous media. This novel process iswell-suited to address the aqueous waste problems present at the Hanfordsite. The separated lithium-aluminate complexes and magnesium-aluminatecomplexes may be beneficially used as glass formers in the production ofvitrified low activity waste (LAW).

The advantages of using lithium salts and/or magnesium salts to removealuminum oxides from aqueous media, are at the very least as follows:(1) the per-pass yield for the precipitated lithium-aluminate complex orthe magnesium-aluminate complex is greater than for a modified Bayerprocess; (2) removal of aluminum oxides by lithium and/or magnesium asdescribed herein does not require seeding or seed recycle; and (3) theprecipitation of lithium-aluminate complexes and magnesium-aluminatecomplexes forms large crystals that may be readily beneficiallyseparated and decontaminated from aqueous media.

SUMMARY OF THE INVENTION

An aspect of the invention is a method for removing soluble aluminumoxides from an aqueous medium comprising contacting a lithium salt withthe media; collecting the resulting precipitated lithium-aluminatecomplex; and optionally washing the collected lithium-aluminate complex.

Another aspect of the invention is a method for removing solublealuminum oxide from an aqueous medium comprising contacting a magnesiumsalt with the media; collecting the resulting precipitatedmagnesium-aluminate complex; and optionally washing the collectedmagnesium-aluminate complex.

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures represent specific embodiments of the inventionand are not intended to otherwise limit the scope of the invention.

FIG. 1 depicts an exemplary embodiment of the invention in which aluminais removed via precipitation from an aqueous media using lithium salts.In this example, the caustic feed solution is heated to a temperature of90° C. and Al(OH)₃ is leached into the feed solution to saturate thesolution with alumina at that temperature. A solution of 40 wt % LiNO₃(lithium nitrate) is added to the saturated solution. The reactionproduces lithium-aluminate complex salts, generally of the formulaLi₂CO₃.2Al(OH)₃.3H₂O. These salts are separated from the solution byfiltration. The filter cake containing the lithium-aluminate salts iswashed on the filter with deionized water to remove impurities from theprecipitate.

FIG. 2 depicts the material balance of the example given in FIG. 1.

FIG. 3 depicts an exemplary embodiment of the invention in which aluminais removed via precipitation from an aqueous media using magnesiumsalts. In this example, the aqueous waste solution containing solubleand insoluble alumina (Al(OH)₃) is heated to a temperature of 90° C. toleach solid alumina into solution. A solution of 40 wt % Mg(NO₃)₂(magnesium nitrate) is added to the solution. The reaction producesmagnesium hydrotalcites (e.g., magnesium carbonate complexes, generallyof the formula Mg₆CO₃Al₂(OH)₁₆.3H₂O). These complexes are separated fromthe solution by filtration. The filter cake containing the hydrotalciteis washed on the filter with deionized water to remove impurities fromthe precipitate.

FIG. 4 depicts the material balance of the example given in FIG. 3.

DETAILED DESCRIPTION OF THE INVENTION Definitions

Unless defined otherwise, all technical and scientific terms used hereingenerally have the same meaning as commonly understood by one ofordinary skill in the art to which this invention belongs.

As defined herein, “lithium” “lithium salt” refers to an organic orinorganic lithium-containing salt that is at least partially soluble inwater. Exemplary embodiments include, but are not limited to, lithiumbicarbonate (LiHCO₃), lithium hydroxide (LiOH), lithium nitrite (LiNO₂),lithium nitrate (LiNO₃), lithium bromide (LiBr), lithium chloride(LiCl), lithium fluoride (LiF), lithium phosphate (Li₃PO₄), lithiumsulfate (Li₂SO₄), lithium acetate (LiAc) and lithium citrate(Li₃C₆H₅O₇.4H₂O).

In an exemplary embodiment of the invention, the lithium salt includes,but is not limited to, Li₂CO₃, LiHCO₃, LiOH, LiNO₂, LiBr, LiCl, LiF,Li₃PO₄, Li₂SO₄, LiNO₃, LiAc and mixtures thereof.

In an exemplary embodiment, the lithium salt is lithium nitrate.

As defined herein, “magnesium” or “magnesium salt” refers to an organicor inorganic magnesium-containing salt that is at least partiallysoluble in water. Exemplary embodiments include, but are not limited to,magnesium bicarbonate (Mg(HCO₃)₂), magnesium hydroxide (Mg(OH)₂),magnesium nitrite (Mg(NO₂)₂), magnesium nitrate (Mg(NO₃)₂), magnesiumbromide (MgBr₂), magnesium chloride (MgCl₂), magnesium fluoride (MgF₂),magnesium phosphate (Mg₃(PO₄)₂), magnesium sulfate (MgSO₄), magnesiumacetate (Mg(Ac)₂) and magnesium citrate (Mg₃(C₆H₅O₇)₂.4H₂O).

In an exemplary embodiment of the invention, the magnesium saltincludes, but is not limited to, MgCO₃, Mg(HCO₃)₂, Mg(OH)₂, Mg(NO₂)₂,MgBr₂, MgCl₂, MgF₂, Mg₃(PO₄)₂, MgSO₄, Mg(NO₃)₂, MgAc and mixturesthereof.

As defined herein, “aluminum oxides” refer to molecules containing bothaluminum and oxygen, in various states of hydration, that are at leastpartially soluble in water. Aluminum oxides include, but are not limitedto, alumina (Al₂O₃), aluminum trihydroxide (hydrated alumina andAl(OH)₃) and aluminum oxy hydroxide (AlO(OH)).

In an exemplary embodiment of the invention, the aluminum oxideincludes, but is not limited to, Al₂O₃, Al(OH)₃, AlO(OH) and mixturesthereof.

In one embodiment of the invention, a lithium salt and/or a magnesiumsalt is utilized to precipitate leached alumina from aqueous media,through the precipitation of lithium-aluminate complexes and/ormagnesium-aluminate complexes, respectively.

In an exemplary embodiment, the leached alumina is in the form of theaqueous aluminate ion (e.g., Al(OH)₄ ⁻¹).

In an exemplary embodiment, the lithium-aluminate complex or themagnesium-aluminate complex is a hydrotalcite.

In exemplary embodiments of the invention, the temperature of theaqueous media during the formation and precipitation of thelithium-aluminate and/or magnesium-aluminate salts ranges from about 35°C. to about 150° C., such as from about 40° C. to about 120° C., such asfrom about 40° C. to about 100° C., such as from about 50° C. to about100° C., such as about 75° C. to 95° C.

In an exemplary embodiment of the invention, the lithium-aluminatecomplexes are crystalline and have the general formula(LiA_(x))_(y).2Al(OH)₃.nH₂O and the lithium-aluminate complexprecipitation reaction is illustrated by the following reaction:

2Al(OH)₄ ⁻¹ +yLiA_(x) +nH₂O→(LiA_(x))_(y).2Al(OH)₃ .nH₂O⁻¹

wherein A is an anion including, but not limited to OH⁻¹, NO₃ ⁻¹, NO₂⁻¹, HCO₃ ⁻¹, Cl⁻¹, F⁻¹, SO₄ ⁻², CO₃ ⁻², PO₄ ⁻³; n is an integer selectedfrom 1 to 3; y is the number of lithium atoms present for each twoaluminum atoms and is an integer selected from 0.5 to 1.2; A is acounterion to the lithium and has a negative valence of 1, 2, or 3; andx is the negative reciprocal of the valence of A (i.e., x is 1, ½ or ⅓,respective to when A is −1, −2 or −3). The presence of the anion A maybe due to the addition of the lithium salt (LiA) to the aqueous media orit may already have been present in the aqueous media before theaddition of the lithium salt.

In an exemplary embodiment, the lithium-aluminate-carbonate complexformed is dilithium carbonate tetra(aluminum trihydroxide) trihydrate(Li₂CO₃·4Al(OH)₃·3H₂O) (“LAHCS”). The source of carbonate includes, butis not limited to, sodium carbonate (Na₂CO₃), sodium bicarbonate(NaHCO₃), potassium carbonate (K₂CO₃), potassium bicarbonate (KHCO₃),lithium carbonate (Li₂CO₃), lithium bicarbonate (LiHCO₃), magnesiumcarbonate (MgCO₃), and carbon dioxide (CO₂). Lithium aluminate carbonatecomplexes are described in U.S. Pat. No. 5,997,836, which isincorporated by reference in its entirety. The overall reaction thatleads to this particular lithium-carbonate-aluminum complex is asfollows, where LiA represents the lithium salt and CO₃ ⁻² represents acarbonate source:

4Al(OH)₄ ⁻¹+2LiA+CO₃ ⁻²+3H₂O→Li₂CO₃·4Al(OH)₃·3H₂O+4OH⁻¹+2A⁻¹

Other anions may be substituted for carbonate in the lithium-aluminatecomplexes, as represented by the following reaction:

4Al(OH)₄ ⁻¹+2LiA+3H₂O→Li₂A·4Al(OH)₃·3H₂O+4OH⁻¹+A⁻¹

where A may be an anion of the group (OH⁻¹, NO₃ ⁻¹, NO₂ ⁻¹, HCO₃ ⁻¹, CO₃⁻², Cl⁻¹, F⁻¹, SO₄ ⁻²). The anion by be donated from the lithium saltadded to the waste, or the anion may be a component of the waste.

The above reaction is reported to occur rapidly at temperatures fromabout 40° C. to about 95° C. and a pH from about 7 to above 14. Thereaction may occur in basic solution where the free hydroxideconcentration is higher than 0.1 molar—i.e., at a pH above about 14.

In an exemplary embodiment, the Al(OH)₃ is in a colloidal (gel) form andan acid (i.e., HNO₃, CO₂) is used to partially neutralize a wastemixture, followed by the addition of a lithium salt (LiA) to precipitatethe alumina as lithium aluminate complexes. Typically, the lithiumaluminate complexes have an isometric crystal habit which allows foreasy separation, deliquoring and decontamination.

In an exemplary embodiment, the formation of lithium-aluminate complexsalts are accomplished by the reaction of the lithium salt with solublealumina, or with alumina in a gel form or solid phase alumina.

In other exemplary embodiments, lithium aluminate complexes can form asolid precipitate in aqueous media when, for the structure

(LiA_(x))_(y).2Al(OH)₃ .nH₂O

wherein

-   A is an anion of negative valence −1, −2, or −3;-   x is the negative reciprocal of the valence A (i.e., x is 1, ½ or ⅓,    respective to A being −1, −2, or −3); 0.1≦y≦1.0; and 0≦n≦10.

Thus, the Li/Al mole ratio can vary from approximately 0.16 to 1.6. Inlow-activity waste (LAW) glass, lithium carbonate is added as a glassformer in the mole ratio of 2:1 Li:Al so that if lithium is used toprecipitate lithium aluminate complexes, there is no net increase in LAWglass volume and the cost impact of adding lithium in thelithium-aluminate process becomes negligible.

In an exemplary embodiment, once the aluminum oxide (for example,alumina) has been precipitated from an aqueous media as alithium-aluminate salt, the aqueous media becomes regenerated inhydroxide (OH⁻¹) by the reaction:

4Al(OH)₄ ⁻¹+2LiA+3H₂O→Li₂A·4Al(OH)₃·3H₂O+4OH⁻¹+A⁻¹

Upon separation of the precipitated lithium-aluminate salt, the aqueousmedia may be recycled for additional aluminum oxide sludge leaching,thereby reducing or eliminating the need for adding large quantities ofsodium hydroxide to dissolve the aluminum oxide sludge.

In an exemplary embodiment, once the aluminum oxide (for example,alumina) has been precipitated from an aqueous media via alithium-aluminate salt and no additional hydroxide is required forfurther alumina leaching, the presence of hydroxide (for example, sodiumhydroxide) is longer necessary in the aqueous media to maintainsolubility of aluminum oxides. Therefore, the remaining hydroxide may bedestroyed by partial neutralization of the solution by the action of anacid:

NaOH+HA_(x)→NaA_(x)+H₂O

where the acid may be organic (such as, for example, acetic acid, citricacid or fumaric acid) or inorganic (such as, for example, hydrochloricacid, sulfuric acid or nitric acid). A may be an anion of the group (NO₃⁻¹, NO₂ ⁻¹, HCO₃ ⁻¹, Cl⁻¹, F⁻¹ CO₂ ⁻², SO₄ ⁻²), and x is the negativereciprocal of the valence of A (i.e., x is 1 or ½ respective when A is−1 or −2).

By neutralization reactions sodium hydroxide is converted to a sodiumsalt thereby lowering the free hydroxide concentration of the solution.Once the highly soluble aluminum and hydroxide salts have been removedfrom the aqueous medium, the viscosity of the medium is significantlylowered allowing simpler downstream processing of the aqueous waste.

In an exemplary embodiment of the invention, the magnesium-aluminatecomplexes are crystalline and have the general formulaMg₆A.Al₂(OH)₁₆.nH₂O and the magnesium-aluminate complex precipitationreaction is illustrated by the following reaction:

2Al(OH)₄ ⁻¹+6MgA_(x)+8OH⁻¹ +nH₂O→Mg₆A_(x).Al₂(OH)₁₆ .nH₂O+(5x)A^(x−3)

wherein A may be an anion including, but not limited to OH⁻¹, NO₃ ⁻¹,NO₂ ⁻¹, HCO⁻¹, Cl⁻¹, F⁻¹, SO₄ ⁻², CO₃ ⁻²; n is an integer selected from1 to 4; A is a counterion to the magnesium and has a negative valence of1 or 2; and x is the valence of A plus three (i.e., x is 2 or 1,respective to when A is −1 or −2). The presence of the anion A may bedue to the addition of the magnesium salt (MgA) to the aqueous media orit may already have been present in the aqueous media before theaddition of the magnesium salt. The hydroxide ion may be present in theaqueous media before the addition of the magnesium salt, it may be addedas an additional salt (e.g. NaOH), or may be supplied by the magnesiumsalt (e.g., Mg(OH)₂).

The above reaction is reported to occur rapidly at temperatures fromabout 40° C. to about 95° C. and a pH from about 7 to above 14. Thereaction may occur in basic solution where the free hydroxideconcentration is higher than 0.1 molar i.e., at a pH above about 14.

In an exemplary embodiment, the solids formed in the reaction betweenthe lithium and alumina can be separated, deliquored and washed byordinary separations equipment (e.g., filters, hydrocyclones, andcentrifuges).

In an exemplary embodiment, the magnesium hydrotalcite complex formed ishexamagnesium carbonate dialuminum hexadecahydroxide trihydrateMg₆CO₃Al₂(OH)₁₆.3H₂O. The source of carbonate includes, but is notlimited to, not limited to, sodium carbonate (Na₂CO₃), sodiumbicarbonate (NaHCO3), potassium carbonate (K₂CO₃), potassium bicarbonate(KHCO₃), magnesium carbonate (MgCO₃), magnesium bicarbonate (Mg(HCO₃)₂),and carbon dioxide. The generalized reaction that leads to thisparticular magnesium-carbonate-hydrotalcite complex is as follows, whereA represents a divalent anion, MgA represents the magnesium salt and CO₃⁻² represents a carbonate source:

4Al(OH)₄ ⁻¹+6MgA+CO₃ ⁻²+8OH⁻¹+3H₂O→Mg₆CO₃Al₂(OH)₁₆•3H₂O+6A⁻²

The above reaction is reported to occur rapidly at temperatures fromabout 40° C. to about 95° C. and a pH from about 7 to above 14. Thereaction may occur in basic solution where the free hydroxideconcentration is higher than 0.1 molar—i.e., at a pH above about 14.

In an exemplary embodiment, the Al(OH)₃ is in a colloidal (gel) form andan acid (i.e., HNO₃, CO₂) is used to partially neutralize a wastemixture, followed by the addition of a magnesium salt (MgA) toprecipitate the alumina as magnesium hydrotalcite complexes. Typically,the hydrotalcite complexes have an isometric crystal habit which allowsfor easy separation, deliquoring and decontamination.

In an exemplary embodiment, the formation of hydrotalcite complexes isaccomplished by the reaction of a magnesium salt or a lithium salt withsoluble alumina, or with alumina in a gel form or solid phase alumina.

In an exemplary embodiment, the formation of hydrotalcite complexes isaccomplished by the reaction of a magnesium salt or a lithium salt withsolid phase alumina in the form of an aluminosilicate gel or solid phasealuminosilicate.

In other exemplary embodiments, magnesium hydrotalcite complexes canform a solid precipitate in aqueous media when, for the structure

(Mg₆A_(x))_(y)Al_(z)(OH)_(m) .nH₂O

wherein

-   A is anion of negative valence 1, 2, or 3;-   x is the valence A plus three (i.e., 2 or 1 respective to A being −1    or −2).-   0.1≦y≦1.0;-   0.1≦z≦6.0;-   0≦m≦20;-   0≦n≦10.    Thus, the Mg/Al ratio can vary from approximately 0.1 to 3. In    low-activity waste (LAW) glass, magnesium silicate is added as a    glass former. Thus, there is no net increase in LAW glass volume and    the cost impact of adding magnesium in the magnesium hydrotalcite    process becomes negligible.

In an exemplary embodiment of the invention, the aqueous media in whichthe reaction with the lithium salts and/or magnesium salts occurs,further includes organic and/or inorganic residues. Inorganic residuesencompass inorganic salts that include, but are not limited to, NaNO₃,NaNO₂, NaAlO₂, Na₂CO₃, Na₂SO₄, NaF, Na₃PO₄, NaOH, KOH, Na₂CrO₄ andmixtures thereof. Organic residues include, but are not limited to,NaCOOH, Na(C₂H₃O,), Na₂C₂O₄, and mixtures thereof.

In an exemplary embodiment of the invention, the aqueous medium isradioactive aqueous waste.

Without further description, it is believed that one of ordinary skillin the art can, using the preceding description and the followingillustrative examples, make and utilize the compounds of the inventionand practice the claimed methods. The following working examplesdescribe embodiments of the present invention, and are not to beconstrued as limiting in any way the remainder of the disclosure.

EXPERIMENTAL Example 1

The purpose of this experiment was to determine the effectiveness of aprecipitating lithium-aluminate complexes in the form of(LiA_(x))_(y).2Al(OH)₃.nH₂O from a waste simulant using lithium nitrateas the lithium salt. Lithium nitrate has a higher aqueous solubilitythan, for example, lithium carbonate. For this experiment, anon-radioactive waste simulant was used with aqueous chemistry similarto typical Hanford double-shell tank (DST) supernatant. The experimentwas designed to maximize the yield of lithium-aluminate complexes and toestimate the rate of precipitation. The DST simulant contained dissolvedinorganic salts such as NaNO₃, NaNO₂, Na₂CO₃, Na₂SO₄, NaF, Na₃PO₄, NaOH,KOH, NaCrO₄ and organic contaminants such as formate, oxalate, acetateand glycolate salts. The anions of these sodium salts may exchange withthe anion of the lithium salt in the lithium-aluminate complexprecipitation. A total of 924.1 g DST simulant solution was added to a 2liter mixing vessel.

Gibbsite Leaching

The contents of the vessel were heated to 100° C., then 81.5 grams ofgibbsite (Al(OH)₃) were added to the vessel to bring it to saturationwith respect to alumina. The solution was mixed until clear.

Lithium Hydroxide Addition

The simulant was then cooled to 90° C. and 175.5 grams of 11 weight %aqueous solution of LiOH at 25° C. was gradually added at approximately2 g/min. The reaction temperature was maintained at 90° C. during the 1hour LiOH addition.

Filtration and Washing

The resulting slurry was cooled to 65° C. and filtered in a büchnerfunnel. Wet cake mass was 384.8 grams. The filter cake was washed with atotal of 2 liters of deionized water at 25° C. Washed cake mass was295.5 grams. Dry cake mass was 179.2 grams resulting in an aluminumyield of 91%. The Li/Al ratio of the cake was 0.71, indicating theformation of lithium-aluminate complexes.

Example 2

The purpose of the experiment was to determine the effectiveness of aprecipitating magnesium hydrotalcite complexes in the form of(Mg₆A_(x))_(y)Al_(z)(OH)_(m).nH₂O from a waste simulant using magnesiumnitrate as the magnesium salt. Magnesium nitrate has a higher aqueoussolubility than, for example, magnesium carbonate. The waste simulant issimilar to the chemical composition in Example 1. The experiment wasdesigned to maximize the yield of hydrotalcite complexes and to estimatethe rate of precipitation. The simulant contained dissolved inorganicsalts such as NaNO₃, NaNO₂, Na₂CO₃, Na₂SO₄, NaOH, KOH, NaCrO₄ andalumina as Al(OH)₃. The anions of the sodium salts may exchange with theanion of the magnesium salt in the magnesium hydrotalcite complexprecipitation. A total of 1926.6 g DST simulant solution was added to a4 liter mixing vessel.

Gibbsite Leaching

The contents of the vessel were heated to 100° C. to dissolve solidphase alumina. The solution was mixed until clear.

Magnesium Nitrate Addition

The simulant was then cooled to 90° C. and 1,232 grams of 41 weight %aqueous solution of Mg(NO₃)₂ at 25° C. was gradually added atapproximately 20 g/min. The reaction temperature was maintained at 90°C. during the 1 hour Mg(NO₃)₂ addition.

Filtration and Washing

The resulting slurry was cooled to 65° C. and filtered in a büchnerfunnel. Wet cake mass was 1784.6 grams. The filter cake was washed witha total of 4 liters of deionized water at 25° C. Washed cake mass was1330 grams. Dry cake mass was 294 grams resulting in an aluminum yieldof 88%. The Mg/Al ratio of the cake was 2.8, indicating the formation ofmagnesium hydrotalcite complexes.

Unless defined otherwise, all technical and scientific terms herein havethe same meaning as commonly understood by one of ordinary skill in theart to which this invention belongs. Although any methods and materials,similar or equivalent to those described herein, can be used in thepractice or testing of the present invention, the preferred methods andmaterials are described herein. All patents, publications and patentapplications cited herein are incorporated herein by reference for thepurpose of disclosing and describing specific aspects of the inventionfor which the publication is cited.

REFERENCES

All documents cited herein are incorporated by reference in theirentireties.

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1. A method for removing soluble aluminum oxides from an aqueous mediumcomprising contacting a lithium salt with the medium; collecting theresulting precipitated lithium-aluminate complex; and optionally washingthe collected lithium-aluminate complex, wherein the aqueous mediumcontains chemically hazardous or radioactive waste.
 2. The methodaccording to claim 1, wherein the lithium salt is selected from thegroup consisting of Li₂CO₃, LiHCO₃, LiOH, LiNO₂, LiCl, LiF, Li₃PO₄,Li₂SO₄, LiNO₃, LiAc and mixtures thereof.
 3. The method according toclaim 1, wherein the lithium salt is LiNO₃.
 4. The method according toclaim 1, wherein the aluminum oxide is selected from the groupconsisting of Al₂O₃, Al(OH)₃, AlO(OH) and mixtures thereof.
 5. Themethod according to claim 1, wherein the aluminum oxide is Al(OH)₃. 6.The method according to claim 1, wherein the aqueous medium furthercomprises a dissolved inorganic salt selected from the group consistingof NaNO₃, NaNO₂, Na₂CO₃, Na₂SO₄, NaF, Na₃PO₄, NaOH, KOH, Na₂CrO₄ andmixtures thereof.
 7. The method according to claim 1, wherein thelithium-aluminate complex is LAHCS.
 8. The method according to claim 1,wherein the temperature of the aqueous medium during the contacting stepis at least about 50° C. to about 100° C.
 9. The method according toclaim 1, further comprising contacting the aqueous medium with amagnesium salt to cause precipitation of a magnesium-aluminate complex.10. A method for removing soluble aluminum oxides from an aqueous mediumcomprising contacting a magnesium salt with the medium; collecting theresulting precipitated magnesium-aluminate complex; and optionallywashing the collected magnesium-aluminate complex, wherein the aqueousmedium contains chemically hazardous or radioactive waste.
 11. Themethod according to claim 10, wherein the magnesium salt is selectedfrom the group consisting of MgCO₃, Mg(HCO₃)₂, Mg(OH)₂, Mg(NO₂)₂, MgCl₂,MgF₂, Mg₃(PO₄)I, MgSO₄, Mg(NO₃)₂, MgAc and mixtures thereof.
 12. Themethod according to claim 10, wherein the magnesium salt is Mg(NO₂)₂.13. The method according to claim 10, wherein the aluminum oxide isselected from the group consisting of Al₂O₃, Al(OH)₃, AlO(OH) andmixtures thereof.
 14. The method according to claim 10, wherein thealuminum oxide is Al(OH)₃.
 15. The method according to claim 10, whereinthe aluminum oxide is an aluminosilicate.
 16. The method according toclaim 10, wherein the aqueous medium further comprises a dissolvedinorganic salt selected from the group consisting of NaNO₃, NaNO₂,Na₂CO₃, Na₂SO₄, NaF, Na₃PO₄, NaOH, KOH, Na₂CrO₄ and mixtures thereof.17. The method according to claim 10, wherein the magnesium-aluminatecomplex is a hydrotalcite.
 18. The method according to claim 10, whereinthe temperature of the aqueous medium during the contacting step is atleast about 50° C. to about 100° C.
 19. The method according to claim10, further comprising contacting the aqueous medium with a lithium saltto cause precipitation of a lithium-aluminate complex.